Metallized tetrakisazo dyes



Patented June 14, 1949 I UNITED STATES PATENT OFFICE METALLIZED TETRAKISAZO DYES Walter Wehrli, Basel, Switzerland, assignor to Sandoz Limited, Basel, Switzerland, a Swiss No Drawing. Application June 12, 1947, Serial No. 754,273. In Switzerland July 14, 1941 8 Claims.

wherein X is hydrogen or'alkyl and R means the radical of Cleves acid, coupling the resultant diazodisazo dyestufi with an azo component of the general formula S OgH NH:

wherein R is a substituted or unsubstituted phenyl radical, and reacting the polyazo dyestuflf thus obtained with a metal yielding agent.

The complex metal compounds of the polyazo dyestufis prepared as herein before defined may further contain groups which are capable of linking metals; in this case, they can be treated with metallizing compounds either in substance or when already dyed on the fibre.

If, instead of the disazo dyestuffs, their metallized derivatives are used as starting materials, the treatment with the metallizing agents can be carried out already with the monoazo dyestufis used for their preparation or with the ready prepared disazo dyestuffs. Under the expression metallizing agents I understand substances which, when applied by usual methods on azo dyestufis containing groups capable of linking metals, transform the dyestufis into their metal complex compounds. Such metallizing agents are for example compounds of copper, nickel, cobalt, chromium, iron, vanadium, and the like. Likewise the metals can be used as such or mixtures of such metal compounds can be used.

The couplingoperation is preferably carried out in the presence of an acid binding agent, such as sodium carbonate, sodium acetate, chalk, calcium hydroxide, pyridine, pyridine bases and the like.

The new dyestuffs obtainable according to my present invention dye cotton, linen and artificial fibres from regenerated cellulose in fast blue-gray shades possessing an excellent aflinity. According to the present method dyeings will be produced which possess good wet-fastness properties an excellent light-fastness properties.

The following examples, without being limitative, illustrate the present invention, the parts being by weight.

Example 1 63.7 parts of the disazo dyestufi of the formula OH on .0... M6... N...

I SOzNa are diazotized with 6.9 parts of sodium nitrite and 25 parts of hydrochloric acid and coupled in the presence of 50 parts of sodium bicarbonate and 50 parts of technical pyridine base mixture with 36.5 parts of a monoazo dyestuff of the formula S OaNa NH:

The dyestufi thus obtained is then salted out and filtered. The precipitate is dissolved in water and transformed into its copper derivative by treating it at an elevated temperature with 25 parts of copper sulfate in the presence of sodium acetate. After salting out, filtration and drying the new dyestufi is a bronzing powder. It dyes cotton and artificial silk from regenerated cellulose in bluish grey shades, which are very fast to light.

The transformation of the polyazo dyestufi into its copper-complex compound can, with the same success, be carried out by treating it with copper sulfate in the presence of ammonia.

Example 2 69.9 parts of the copper compound of the disazo dyestufl of the formula on 0H MQN.

'S O Na NH:

with 44.7 parts of the monoazo dyestufl 01' the formula.

6 coin in presence of sodium bicarbonate and tenants:

wherein X is a'niernloeriselected'ifroni the, grcup consisting of hydrogen and alkyl and 1?; means the radical bi 'cleve acid, coupling i t i rf'siiii'aiit diazodisazo dyestufi with an azo component or the general formula wherein R is a member selected from the group consisting of unsubstituted and substituted phenyl radicals, and interacting the polyazo dyestufi thus obtained with a metal xyiel'dingfagent.

1 stuff, comprising the steps of diazotizing a disazo dyestuff of the formula OH OH wherein "X is a. member selected .from the'group consisting of hydrogen andalkyi and 'R means we radical 'of Cleves acid, coupling ther'esultant diaz oclisazo dyestufi with an azo component of the general formula wherein R. is a member selected frrbm the group consisting of unsubstituted and. substituted phenyl ra c 1icals, ancl interacting the polyazo dyestufi thus iohtaiiieti with a copper yielding agent;

fA* raess for the manufactured the'honi- *mextapter 'conipound of the js'uh'st'antive iioiyako dyestufi of the following formula "on on 2. A process forthe"manufactureioia complex copper compound of a substantive polyazo dye- -:'in5risisg-* the stepsof dia'zoting me amaze aiss'nin cf the formula taming" the} resultant 'giisztai'stz ateaasmth 'themonoazo dyestuff of the formula and interacting the resultant polyazo iiye stu ff with a,tamperz/yieliiin .ELE IJLv 4. A process for the manufacture of the comammo-u plex'copper compound of thesubstantive'polyazo compound dyes cellulose fibres in i'ast blue-grey dyestufi of the following formula shades.

comprising the steps of diazotizing the disazo dye- 6. A complex copper compound or a substantive stuff of the formula polyazo dyestufi of the formula coupling the resultant diaaodisazo dyestufl with the monoazo dyestuii' of the formula wherein X is a member selected from the group consisting of hydrogen and alkyl, R means the SOIH NH: radical of Cleves acid and R is a, member selected from the group consisting of substituted and un- N=N- 0H substituted phenyl radicals, which complex copper compound dyes cellulose fibres in fast blue- 0011 grey shades. and interacting the resultant polyazo dyestui! 7. The complex copper compound of the subwith a copper yielding agent. stantive polyazo dyestufi of the formula on on 5. A complex metal compound of a substantive NH! polyazo dyestufi of the formula 803E BIO-O OH OH 8 01H on X 801K NH I which complex copper compound dyes cellulose fibres in fast bluish-grey shades.

wherein X is a member selected from the group 8. The complex copper compound of the subconsisting of hydrogen and alkyl, R means the stantive polyazo dyestufi of the formula which complex copper compound dyes cellulose radical of Cleves acid and R is a member selected fibres in greenish ey'blue shadesfrom the group consisting of substituted and un- WALTER WEHRH- substituted phenyl radicals, which complex metal (References on following page) r ,REFERENCES"CITED Number Date 2 203 196 Hanhart Hum-m June 4 1940 .v a 5 g i g g f ffi are in the 2,215,097 Schweitzer Sept. 1'1, 1940 TES TENTS 2,270,675 Stein et a1 Jan. 20, 1942 UNITED STA PA 5 9 Number Name Date FoRmGN PA TS- 1,829,672 Richard Oct. 27, 1991 -N1imber Country-9 Date 2,180,245 Krebser Nov. 14, 'Frafice Oct. i0, 1938 

